Polyvinyl alcohol composition and film

ABSTRACT

A method of preparing a plasticised particulate polyvinyl alcohol (PVA) composition is provided, comprising: mixing, in a mixer, at a mixer speed and for a time sufficient that the mixture attains a temperature of at least 50° C.: particulate PVA resin in an amount from 80% to 90% by weight of the mixture; and plasticiser in an amount from 10% to 20% by weight of the mixture, wherein at least a portion of the plasticiser is water; monitoring the apparent viscosity of the mixture during mixing and continuing mixing until the apparent viscosity of the mixture has peaked to a maximum and dropped off to a substantially constant level, thereby to obtain a plasticised particulate mixture having a moisture content in the range from 7% to 14%; preferably adding an anti-caking agent in an amount from 0.05% to 0.5% by weight of the plasticised particulate mixture, and continuing mixing until the anti-caking agent is blended to the plasticised particulate mixture; and stopping mixing, and removing the mixture from the mixer, wherein the mixture temperature is kept below 100° C. at all times during mixing. The properties of the plasticised particulate composition are such that it can be processed, by extrusion and blowing, to a film having advantageous characteristics in terms of structure and properties. Accordingly, also provided is a PVA film characterised in that, when viewed using polarising light microscopy, it has a nonuniform texture consisting of distinct short range areas, e.g. 10 to 500 micrometers, each short range area showing anisotropic orientation within its area, each short range area being oriented isotropically.

This invention relates to plasticised particulate polyvinyl alcohol(PVA) compositions suitable for forming extruded blown films which arebiodegradable and, hence, environmentally friendly alternatives to filmsformed from polyethylene and other synthetic resins.

Transparent polyethylene films have long been known and used aspackaging material, for example as carrier or refuse bags. Typically,these films have a minimum thickness of about 10 μm, in order to providethe necessary strength and integrity for practical use. However, a majordrawback of these films is that they are generally not biodegradable.

On the other hand, paper is known as a biodegradable packaging material.However, paper generally is opaque and, therefore, for manyapplications, is not suitable. In addition, uncoated paper rapidly losesstrength or integrity under an atmosphere of high relative humidity orunder damp storage conditions, whereas treatments, such as coatings toenhance paper's resistance to moisture, add cost and/or reduce itsbiodegradability.

Biodegradable PVA materials formed from polyvinyl alcohol resinplasticised with glycerol and water are also known. However, attempts tomanufacture extruded blown PVA films have hitherto not been successfulfor practical purposes, in that these PVA films were found to sufferfrom lack of clarity or transparency, discolouration e.g. yellowing or,in extreme cases, browning, and, in particular, high manufacturing cost.A further disadvantage of these films is that residual methanoloriginally present in the PVA raw material is generally still present inthe films, and this is undesirable for health and safety reasons due tothe toxic nature of methanol.

It would therefore be desirable to provide an improved biodegradable PVAfilm, that is useful in practice as an environmentally friendlypackaging material, for example as carrier or refuse bags, and thateliminates or reduces the problems associated with the PVA films knownin the art.

We have now found that it is possible to provide biodegradable PVA filmsthat meet the requirements for practical use as packaging material, interms of production cost, mechanical strength properties,biodegradability, elimination of residual methanol, and aestheticcharacteristics such as lack of discolouration and improved clarity.This has been achieved by providing a plasticised particulate PVAcomposition in accordance with the present invention, that is useful forproducing PVA films.

Accordingly, in one aspect of the present invention, method of preparinga plasticised particulate PVA composition comprising:

-   -   mixing, in a mixer, at a mixer speed and for a time sufficient        that the mixture attains a temperature of at least 50° C.:        -   particulate PVA resin in an amount from 80% to 90% by weight            of the mixture; and        -   plasticiser in an amount from 10% to 20% by weight of the            mixture, wherein at least a portion of the plasticiser is            water;    -   monitoring the apparent viscosity of the mixture during mixing        and continuing mixing until the apparent viscosity of the        mixture has peaked to a maximum and dropped off to a        substantially constant level, thereby to obtain a plasticised        particulate mixture having a moisture content in the range from        7% to 14%; and    -   stopping mixing, and removing the mixture from the mixer,        wherein the mixture temperature is kept below 100° C. at all        times during mixing.

In second aspect of the present invention, a plasticised particulate PVAcomposition as produced by the above method is provided.

The plasticised PVA particles thus obtained are suitable for blowing toa film that is biodegradable whilst exhibiting excellent strength andtransparency characteristics. Therefore, in a third aspect of thepresent invention, a PVA film is provided formed from a plasticisedparticulate PVA composition as defined above. According to this aspect,a PVA film is provided comprising a PVA resin in an amount from 80% to90% by weight and plasticiser in an amount from 10% to 20% by weight,characterised in that, when viewed using polarising light microscopy, ithas a nonuniform structural appearance consisting of distinct shortrange areas, each short range area showing anisotropic orientationwithin its area (as evidenced by a uniform colour when viewed usingpolarising light microscopy), each short range area being orientedisotropically (as evidenced by different areas having different colourswhen viewed using polarising light microscopy).

The PVA resin preferably has a mol % hydrolysis figure of 74 to 94, andmay be selected according to the end product desired. For a cold watersoluble product, a mol % hydrolysis figure of 80 to 90 is preferred,whilst for a hot water soluble and compostable product, a mol %hydrolysis figure of 98 to 100, e.g. about 99, is preferred. Preferably,the PVA resin is chosen to be hot water soluble and compostable. It maybe desirable to blend two or more polyvinyl alcohol compositions toobtain the correct properties, for example a product with a mol %hydrolysis value of 98 and a viscosity of 56 mPa·s and a product with amol % hydrolysis value of 99 and a viscosity of 28 mPa·s.

The PVA resin is preferably present in the particulate PVA compositionin an amount from 80% to 90%, more preferably from 82% to 86%, by weightof the composition. The PVA resin component may include up to 5% ofwater, by weight of the PVA resin component.

The number average particle size of the PVA resin is suitably in therange from 0.5 mm to 1.0 mm, distributed for example over a range with aminimum particle size of 0.1 mm and maximum particle size 2 mm.

Suitable PVA resin materials, of various grades and degrees ofhydrolysis, are known and available from commercial suppliers, andinclude those sold under trade names Gohsenol® (ex Nippon Gohsei),Poval® (ex Kuraray), and Celvol® (ex Celanese).

The plasticiser is present in the particulate PVA composition in orderto plasticise the PVA resin particles. The plasticiser comprises atleast water, and preferably further comprises one or more otherplasticising compounds. The plasticiser is preferably formed of waterand one or more di-, tri- and poly-hydric alcohols, esters, ethers andalkylamines having a chain length of 3 to 14 carbon or hetero atoms(excluding OH groups) in the longest chain. More preferably, theplasticiser is a mixture of water and one or more of glycerol, ethyleneglycol, diethylene glycol, triethylene glycol, polyethylene glycolhaving an average molecular weight of less than 200, trimethylolpropane, neopentyl glycol and triethanolamine. Most preferably, theplasticiser consists of water and glycerol.

Water constitutes preferably 25% to 100%, more preferably 40% to 60%, byweight of the plasticiser. In a preferred embodiment, the plasticiserconsists of water in an amount from 25% to 62.5% and glycerol in anamount from 37.5% to 75% by weight of the plasticiser.

In the preferred case that the plasticiser consists of water andglycerol, we prefer that the glycerol is present in an amount from 6% to12%, preferably from 8% to 9%, by weight of the composition beforeplasticisation, and that the water is present in an amount from 4% to10%, preferably from 5% to 10%, by weight of the composition. The weightratio of glycerol to water is preferably in the range from 0.8:1 to 2:1,more preferably in the range from 1.3:1 to 1.7:1.

If the total amount of plasticiser is below 10%, films produced from thecomposition may not be sufficiently plasticised, and thus will tend tobe brittle, difficult to process, and suffer from lack of clarity anddiscolouration.

If the amount of plasticiser is above 20%, the films tend to be tackyand may stick to each other (‘blocking’), or the plasticiser may beleached or migrate out of the film. If water is present in excessiveamount, bubbles may appear in the film (‘fish-eye’ defects) due toboiling of the water during extrusion.

The amount of water included in mixture of PVA and plasticiser iscontrolled to provide a moisture content in the plasticised particulatecomposition in the range from 7% to 14%, for example in the range from7% to 11%. It will be appreciated that the PVA resin, as supplied, mayalready contain small amounts of water, for example up to weight % ofthe resin, which can contribute to plasticisation. Thus, the amount ofwater included as added plasticiser in the mixture should be adjustedaccordingly to take account of the water content in the raw PVA resin,so as to provide a moisture content in the plasticised particulatecomposition in the range from 7% to 14%, for example in the range from7% to 11%.

Accordingly, in another aspect, a plasticised particulate PVAcomposition is provided, comprising particulate PVA resin in an amountfrom 80% to 90% by weight; glycerol in an amount from 6% to 12% byweight; water in an amount from 4% to 10% by weight; and an anti-cakingagent in an amount from 0.05% to 0.5% by weight, wherein the moisturecontent of the plasticised particulate PVA composition is in the rangefrom 7% to 14%, for example in the range from 7% to 11%.

Preferably, the method according to the invention further comprisesadding an anti-caking agent to the plasticised mixture, when theapparent viscosity of the mixture has begun to drop off from itsmaximum. Mixing is then continued until the anti-caking agent is blendedto the plasticised particulate mixture. The anti-caking agent ispreferably added so that it is present in the particulate PVAcomposition in an amount from 0.05% to 0.5%, more preferably from 0.1%to 0.3%, by weight of the plasticised composition. Preferably, fumedsilica is used as the anti-caking agent. Suitable fumed silica isavailable as Aerosil® R972 (ex Degussa). If no anti-caking agent isadded, or if the amount of fumed silica is below 0.05%, this may tend tolead to caking, whilst no significant benefits are obtained byincreasing the amount of firmed silica above 0.5%.

If desired, colouring or opacifying agents, or the like, may optionallybe included in the composition, preferably after plasticising of thecomposition. These may be included in total amounts of, for example, 1to 3% by weight of the plasticised composition. Preferably, no colouringor opacifying agents are present in the composition, in order to ensurea clear, transparent film after processing.

During mixing of the PVA resin, plasticiser and, if added, finnedsilica, the mixture temperature should be kept below 100° C., preferablybelow 90° C., at all times. This is to prevent boiling off of any waterpresent in the plasticiser, and to prevent the PVA dissolving in thewater with consequent coagulation or caking of the PVA particles tolumps on cooling.

Surprisingly, effective plasticisation can be achieved at temperaturesbelow 100° C., even at temperatures as low as 60° C., for example attemperatures in the range from 70° C. to 90° C. Importantly, thecompletion of the plasticising stage can be determined by monitoring theapparent viscosity of the mixture during mixing, for example by trackingthe motor load of the mixer. By ‘apparent viscosity’ is meant theresistance to shear mixing provided by the particulate mixture. As themixture is worked in the mixer, through friction and shear, itstemperature increases, and a suitable mixing speed and time should beselected to ensure that the mixture reaches a temperature of at least50° C., more preferably at least 60° C., to facilitate plasticisation.The plasticisation phase is manifested, during mixing, by a gradualincrease in the apparent viscosity of the mixture, to a maximum apparentviscosity, followed by a rapid drop-off to a constant level. Throughoutthe plasticisation phase, the mixture temperature continues to rise.Following the apparent viscosity drop-off, further mixing does not causesignificant further changes in the apparent viscosity of the plasticisedmixture, although the mixture temperature would continue to rise throughfriction and shear mixing. The changes in apparent viscosity areaccompanied by a corresponding increase and decrease in mixture volume.Typically, the plasticisation phase occurs over a period of 5 to 10minutes, based on a 70 kg batch mixed at the high speed setting of atwo-speed Baker Perkins Hydisperser® mixer, and can be observed by anincrease in motor load from an original current load of about 25A to amaximum of over 40 A, and drop-off to about 30 A.

Preferably, at approximately the point when the apparent viscosity isdropping off towards a constant level, at which point plasticisation isoptimal, an anti-caking agent such as fumed silica is added and blended.Preferably, the anti-caking agent is added after, and preferably as soonas possible after, the apparent viscosity has begun to drop off from themaximum apparent viscosity level. In one embodiment, the fumed silica isadded to the mixer when the plasticised mixture has attained atemperature in the range from 70° C. to 75° C. When, and preferably assoon as possible after, the anti-caking agent has been blendedsufficiently to prevent caking of the plasticised particles, the mixingis stopped and the blend is removed from the mixer.

Further mixing and blending after the plasticisation phase is possible,but less desirable, and always provided that the mixture temperature iskept below 100° C.

It is preferred to chill or cool the plasticised particulate mixture, orallow the mixture to cool, and store it before passing it to theextruder. Typically, a temperature of 5° C. to 35° C., e.g. about 20° C.is suitable.

If desired, after cooling, the plasticised particulate composition maybe tumbled in order to disperse any moisture that might have accumulateddue to the hydrophilic nature of the PVA, and/or sieved to remove anyclumps.

The properties of the plasticised particulate composition produced bythe method according to the invention are such that it can be processed,by extrusion and blowing, to a film having advantageous characteristicsin terms of structure and properties.

For further processing to a film, the plasticised particulatecomposition may be extruded through a die, and blown, using conventionalapparatus. For example, extrusion can take place in a general purposescrew extruder having controlled zonal heating to give a temperatureprofile along the barrel. A typical example of such an extruder is astandard commercially available 38 mm Betol extruder, ex Betol, Luton,England. A typical apparatus has a 2:1 compression and should preferablybe operated at maximum screw speed. The die may be of any appropriategeometry for a film shape and thickness.

Preferably, the plasticised composition is processed through theextruder at a temperature sufficient to oxidise residual methanol thatmay be present in the PVA resin starting material, for example at atemperature, in one or several of the extruder zones, of at least 185°C., preferably at least 190° C., and more preferably at least 195° C.,but preferably not exceeding 210° C.

In a preferred embodiment, the temperature profile is for the barrel tohave four zones in sequence running at about 100° C., about 175° C.,about 190° C. and about 195° C., leading to an adapter also running atabout 195° C. leading to the die operated at typically 185° C. to 195°C.

The PVA film comprises PVA resin in an amount from 80% to 90% by weightand plasticiser in an amount from 10% to 20% by weight, and exhibitscharacteristic features when viewed using polarising light microscopy.In particular, it has a regular nonuniform texture, in that theappearance is of a mesh or web-like, speckled, grainy or mottledstructure, and is therefore not uniformly smooth. This structuralappearance is regular across the extent of the film. The nonuniformtexture consists of distinct short range areas, as evidenced bydifferent colours when viewed using polarising light microscopy,corresponding to different short range areas. The short range areas aretypically 10 to 500 micrometers in length and width Each short rangearea shows anisotropic orientation within its area, as evidenced by auniform colour within a particular short range area, when viewed usingpolarising light microscopy. Each short range area is orientedisotropically with respect to the other short range areas, as evidencedby different areas having different colours when viewed using polarisinglight microscopy. When a sample of the film is viewed under rotation,using polarising light microscopy, each short range area changes colouruniformly according to the angle of rotation, thereby indicatinganisotropy in the structure within each area. However, colour changeacross the film is nonuniform, and instead is patchy corresponding tothe short range areas. The overall colour averaged across the film alsochanges with angle of rotation, indicating a more long-range anisotropyin the structure of the film which might be due to directional stressesimparted to the film during extrusion.

The distinctive regular, nonuniform textured structure of the film,consisting of isotropically oriented short range areas of anisotropicstructure, imparts surprising strength, transparency and otherproperties to the film.

The film can be used for all the purposes where polyethylene film istypically useful but possesses the following distinct advantagescompared with polyethylene film:

-   1. The material is anti-static.-   2. It has a higher strength and puncture resistance.-   3. The material has a much lower fire risk, being less inflammable    and producing less toxic fumes when burnt.-   4. The material is totally compostable, hot water soluble or cold    water soluble as required, and recyclable via aqueous solution for    other applications.

The invention will be further illustrated by the following non-limitingexamples:

EXAMPLES Example 1

Preparation of Particulate PVA Compositions:

Composition 1:

Materials:  60 kg PVA resin (Gohsenol&reg; N-300 (fully hydrolysed))  6kg Glycerol  4 kg Water 100 g Fumed silica (Aerosil&reg; R972, exDegussa)

The dry powder PVA resin material at ambient temperature and aplasticiser premixture of the glycerol and water were introduced in bulkinto a two-speed Baker Perkins Hydisperser® high shear mixer that hadbeen preheated to 75° C. and switched to the lower speed setting. Themixture was blended at the lower speed setting, without impartingsignificant shear, for 5 minutes before switching the mixer to thehigher speed setting.

Mixing was continued, for about a further 10 minutes, until the motorload of the mixer, corresponding to apparent mixture viscosity, hadpeaked to a maximum and dropped off to a constant level. At this point,the mixture temperature was approximately 73° C. The fumed silica wasadded and blended for about a further 1 minute. As soon as the fumedsilica was sufficiently blended, mixing was stopped and the plasticisedmixture was removed from the mixer, having attained a temperature ofabout 78° C.

The motor load and temperature profiles against time, from initialaddition of PVA resin and plasticiser premix to the mixer, weremonitored and recorded as shown in Table 1: TABLE 1 Time (min) 0 5 11 1214 14.5 15 16 17 19 Temp 25 36 52 56 66 68 71 73 77 78 (° C.) Load 21 2125 27 35 42 36 32 32 32 (A)

The plasticised powder mixture was allowed to cool overnight, to ambienttemperature, briefly tumbled in a tumble mixer to disperse anyaccumulated moisture, and sieved to remove any clumps.

A white particulate plasticised PVA composition was obtained(“Composition 1”), having a moisture content of 9.8% and number averageparticle size of 0.8 mm.

Composition 2:

Materials:  60 kg PVA resin (Poval&reg; 117H)  6 kg Glycerol  4 kg Water100 g Fumed silica (Aerosil&reg; R972, ex Degussa)

The materials were mixed in the same manner as described forComposition 1. A white particulate plasticised PVA composition wasobtained (“Composition 2”), having a moisture content of 10.0%.

Composition 3:

Materials:  60 kg PVA resin (Celvol&reg; 125)  6 kg Glycerol  7 kg Water100 g Fumed silica (Aerosil&reg; R972, ex Degussa)

The materials were mixed in the same manner as described forComposition 1. A white particulate plasticised PVA composition wasobtained (“Composition 3”), having a moisture content of 13.0%.

Composition 4:

Materials:  60 kg PVA resin (Celvol&reg; 325)  6 kg Glycerol  5 kg Water100 g Fumed silica (Aerosil&reg; R972, ex Degussa)

The materials were mixed in the same manner as described forComposition 1. A white particulate plasticised PVA composition wasobtained (“Composition 4”), having a moisture content of 12.5%.

Composition 5:

Materials:  60 kg PVA resin (Poval&reg; 117)  6 kg Diethylene glycol  4kg Water 100 g Fumed silica (Aerosil&reg; R972, ex Degussa)

The materials were mixed in the same manner as described forComposition 1. A white particulate plasticised PVA composition wasobtained (“Composition 5”), having a moisture content of 13.0%

Composition 6:

Materials:  60 kg PVA resin (Poval&reg; 117H)  10 kg Water 100 g Fumedsilica (Aerosil&reg; R972, ex Degussa)

The materials were mixed in the same manner as described forComposition 1. A white particulate plasticised PVA composition wasobtained (“Composition 6”), having a moisture content of 15.0%.

Example 2

Processing to Form Blown Films:

The particulate PVA composition of Composition 1 of Example 1 wasprocessed to form blown films, using conventional extruder, die andblowing apparatus. The extruder (38 mm Betol general purpose screwextruder) and die temperature profile were as indicated in Table 2:TABLE 2 Zone 1 Zone 2 Zone 3 Zone 4 Adapter Die 100° C. 175° C. 190° C.195° C. 195° C. 195° C.

The screw speed was set initially to 28 rpm, until the mix reached thedie, then adjusted to 100 rpm.

Two PVA films were blown, and assessed against two conventionalpolyethylene (PE) films. Samples of the PVA films and PE films weretested at 23° C. at 50% relative humidity, after having been conditionedby storage for one week at 23° C. at either 50% (“23/50”) or 90%(“23/90”) humidity.

Test methods were as follows:

Thickness: BS2782:6, method 630A (1994), digital deadweight micrometer,29 mm² pressure foot area under a force of 0.85N.

Impact resistance (puncture test): ASTM D1709-91, specimens clamped inannular holder, darts with hemispherical heads loaded with weights weredropped from set distance 66 cm onto centre of clamped specimen, impactresistance taken as the mass in grams of the dart expected to break halfof a number of test pieces.

Tensile strength: BS2782:3, method 326C 1977(1983), Hounsfield tensiletester with internal extensometer, 15 mm wide test pieces, initial jawseparation 50 mm, 500 mm/min test speed, 50 N load cell.

Internal tear resistance: BS EN 21974(1994)/ISO 1974(1990), digitalsingle tear tester, single ply test pieces.

The results are shown in Tables 3 to 7 below: TABLE 3 Thickness (μm)Impact resistance (g) Conditioning Film — 23/50 23/90 23/50 23/90 PVAfilm 1 25 26 29 355 675 PVA film 2 40 41 44 775 1100 PE film 1 62 83 83400 340 PE film 2 100 109 106 380 380

TABLE 4 Yield strength Machine direction Cross direction ConditioningFilm 23/50 23/90 23/50 23/90 PVA film 1 23 12 25 8 PVA film 2 21 7 25 12PE film 1 11 11 10 10 PE film 2 11 13 11 13

TABLE 5 Ultimate tensile strength Machine direction Cross directionConditioning Film 23/50 23/90 23/50 23/90 PVA film 1 68 49 57 50 PVAfilm 2 64 27 66 38 PE film 1 23 22 21 20 PE film 2 23 26 26 25

TABLE 6 Elongation Machine direction Cross direction Conditioning Film23/50 23/90 23/50 23/90 PVA film 1 98 132 228 331 PVA film 2 178 190 256353 PE film 1 539 743 729 802 PE film 2 698 867 893 774

TABLE 7 Internal Tear Resistance Machine direction Cross directionConditioning Film 23/50 23/90 23/50 23/90 PVA film 1 611 856 2449 3277PVA film 2 4445 5276 9094 5850 PE film 1 1718 1500 3261 3082 PE film 22585 2710 2614 4143

The results show that PVA films in accordance with the inventionexhibited superior tensile strength and puncture resistance to the PEfilms, despite PE films 1 & 2 being two and a half times as thick as PVAfilms 1 & 2, respectively.

Further, by visual assessment PVA films 1 & 2 exhibited improved clarityand lack of discolouration compared with PE films 1 & 2. In addition,the PVA films contained no residual methanol.

Example 3

PVA films were blown from particulate plasticised Compositions 2 to 6 ofExample 1, using conventional extruder, die and blowing apparatus, inthe same manner as described for Example 2.

Acceptable films were obtained from Compositions 1 to 5. The film fromComposition 6 contained bubbles.

When viewed statically using polarising light microscopy, the films fromCompositions 1 to 4 appeared as a mesh-like texture of different colourpatches. When viewed under rotation, using polarising light microscopy,the appearance of the films changed colour nonuniformly with angle ofrotation.

Example 4

PVA films were blown from particulate PVA composition of Composition 1of Example 1, using conventional extruder, die and blowing apparatus, inthe same manner as described for Example 2. The films thus prepared(“PVA film 3”) were assessed against two conventional PVA films(“Aquafilm”—Pink Laundry Bag; “PVAXX”—Non-coloured Bag). Samples of thePVA films, each 30 μM in thickness, were tested at 23° C. at 50%relative humidity, after having been conditioned by storage for one weekat 23° C. at 50% relative humidity for at least 16 hours.

Test methods were as follows:

Tensile strength: BS2782:3, method 326C 1977(1983), Hounsfield tensiletester, 15 mm wide test pieces, initial jaw separation 100 mm, 500μm/min test speed, 50 N load cell, 10 replicate tests per direction(machine direction MD, cross direction CD). TABLE 8 Tensile strength andstretch Strength (N/mm²) Elongation (%) Sample Direction Mean MeanAquafilm MD 62 111 CD 58 189 PVAXX MD 45 223 CD 38 266 PVA film 3 MD 69141 CD 61 167

The PVA film 3 showed increased strength in both machine and crossdirections, compared with the Aquafilm and PVAXX films.

When viewed statically using polarising light microscopy, the Aquafilmand PVAXX films appeared smooth and essentially uniform in colour. ThePVA film 3 appeared as a mesh-like structure of different colourpatches.

When viewed under rotation, using polarising light microscopy, theappearance of the Aquafilm and PVAXX films changed colour uniformly withangle of rotation. The appearance of the PVA film 3 changed colournonuniformly on rotation.

1-22. (canceled)
 23. A PVA film produced by a method comprising: mixing,in a mixer, at a mixer speed and for a time sufficient that the mixtureattains a temperature of at least 50° C.: particulate PVA resin in anamount from 80% to 90% by weight of the mixture; and plasticizer in anamount from 10% to 20% by weight of the mixture, wherein at least aportion of the plasticiser is water; monitoring the apparent viscosityof the mixture during mixing and continuing mixing until the apparentviscosity of the mixture has peaked to a maximum and dropped off to asubstantially constant level, to obtain a plasticised particulatemixture having a moisture content in the range from 7% to 14%; stoppingmixing, and removing the mixture from the mixer, wherein the mixturetemperature is kept below 100° C. at all times during mixing; andprocessing the plasticized particulate PVA composition to a film througha temperature zone of at least 185° C., wherein the film is free ofresidual methanol.
 24. A PVA film comprising a PVA resin in an amountfrom 80% to 90% by weight and plasticizer in an amount from 10% to 20%by weight, wherein, when viewed using polarising light microscopy, thefilm has a nonuniform texture consisting of distinct short range areas,each short range area showing anisotropic orientation within its area(as evidenced by a uniform colour when viewed using polarising lightmicroscopy), each short range area being oriented isotropically (asevidenced by different areas having different colours when viewed usingpolarising light microscopy).
 25. The PVA film of claim 24 wherein theshort range areas are 10 to 500 micrometers in length and width acrossthe film.